CN106459754B - Red-emitting phosphors and related devices - Google Patents

Red-emitting phosphors and related devices Download PDF

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CN106459754B
CN106459754B CN201580031387.XA CN201580031387A CN106459754B CN 106459754 B CN106459754 B CN 106459754B CN 201580031387 A CN201580031387 A CN 201580031387A CN 106459754 B CN106459754 B CN 106459754B
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phosphor
particles
combinations
precursor
fluorine
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CN106459754A (en
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J.E.墨菲
A.A.塞特卢尔
F.加西亚
S.P.西斯塔
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Karent lighting solutions Co.,Ltd.
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General Electric Co
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Abstract

Synthetic manganese (Mn)4+) The method of doping a phosphor comprises grinding particles of a phosphor precursor of formula I and contacting the ground particles with a fluorine-containing oxidizing agent at an elevated temperature, Ax[MFy]:Mn4+(I) Wherein A is Li, Na, K, Rb, Cs or a combination thereof; m is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is [ MFy]The absolute value of the charge of the ion; y is 5, 6 or 7.

Description

Red-emitting phosphors and related devices
Background
Based on Mn4+Red emitting phosphors of activated complex fluoride materials, such as those described in US 7,358,542, US 7,497,973, and US 7,648,649, may be used in combination with yellow/green emitting phosphors (e.g., YAG: Ce) or other garnet compositions to achieve a warm white light (CCT on blackbody locus) from a blue LED<5000K, Color Rendering Index (CRI)>80) Which is equivalent to that produced by current fluorescent, incandescent and halogen lamps. These materials strongly absorb blue light and emit efficiently between about 610-635 nm with little deep red/NIR emission. Thus, it emits light in comparison with the red phosphorThe light efficiency is maximized and the red phosphor has a pronounced emission in the deeper red where eye sensitivity is weak. The quantum efficiency can exceed 85% under the excitation of blue (440-460 nm).
Although Mn is used4+The efficacy and CRI of fluoride host doped illumination systems can be high, but one possible limitation is that they are susceptible to degradation under High Temperature and High Humidity (HTHH) conditions. Post-synthesis treatment steps may be used to reduce this degradation, as described in US 8,252,613. However, it is desired to further improve the stability of the material.
Brief description of the invention
Briefly, in one aspect, the present invention relates to a method of synthesizing manganese (Mn)4+) A method of doping a phosphor. Grinding the formula I phosphor precursor to a desired particle size and then contacting it with a fluorine-containing oxidizing agent at an elevated temperature to form Mn4+Doped phosphors
Ax[MFy]:Mn4+ (I)
Wherein
A is Li, Na, K, Rb, Cs or the combination thereof;
m is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof;
x is [ MFy]The absolute value of the charge of the ion;
y is 5, 6 or 7.
In another aspect, the invention relates to Mn preparable by such a process4+A doped phosphor, and including Mn4+Phosphor-doped lighting devices and backlights.
Drawings
These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawings, wherein:
fig. 1 is a schematic cross-sectional view of a lighting device of one embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view of a lighting device according to another embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view of a lighting device of yet another embodiment of the present invention.
Fig. 4 is a cutaway side perspective view of a lighting device of one embodiment of the present invention.
Fig. 5 is a perspective schematic view of a Surface Mount Device (SMD) backlight LED.
Detailed Description
Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as "about," is not to be limited to the precise value specified. In some cases, the approximating language may correspond to the precision of an instrument for measuring the value. In the following specification and claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.
In the method of the present invention, the phosphor precursor is ground, followed by treatment of the ground particles to increase the resulting Mn4+The performance and stability (quantum efficiency, thermal stability, humidity stability and luminous flux stability) of the doped phosphors. The phosphor precursor is ground (milled) to reduce particle size for desired properties. For example, as the phosphor particle size decreases, the settling rate (or deposition rate) of the particles in the encapsulant material (e.g., silicone) decreases. By controlling the particle size and particle size distribution, the settling rate of the particles can be adjusted to match, slower or faster than the other phosphors in the mixture, and thus the phosphor separation can be controlled. Segregation of the phosphor may be advantageous for Mn4+The doped phosphor is protected from damage caused by the excitation flux. In addition, the amount and location of the phosphor particles (closer to or further from the LED chip) can be controlled in order to achieve the desired color point. Additionally, the small particle size (D50 particle size less than 30 microns) may allow for the use of simple deposition techniques, such as spray coating techniques.
The phosphor precursor is Mn of formula I4+A doped complex fluoride material. In the context of the present invention, the term "complex fluoride material or phosphor" refers to a coordination compound containing at least one coordination center surrounded by fluoride ions as ligands and optionallyCharge compensation is performed by the counter ions. In one embodiment K2SiF6:Mn4+In (3), the coordination center is Si and the counterion is K. Complex fluorides are sometimes written as combinations of simple binary fluorides, but such representation does not indicate the coordination number of ligands around the coordination center. Brackets (sometimes omitted for simplicity) indicate that the complex ion it contains is a new chemical species other than a simple fluoride ion. Activator ion (Mn)4+) Also as coordination centers, replacing part of the center of the host lattice, such as Si. The host lattice (including the counter ion) may further modify the excitation and emission properties of the activator ion.
In particular embodiments, the coordination center of the precursor, i.e., M in formula I, is Si, Ge, Sn, Ti, Zr, or a combination thereof. More particularly, the coordination center is Si, Ge, Ti, or a combination thereof, the counter ion or A in formula I is Na, K, Rb, Cs, or a combination thereof, and y is 6. Examples of precursors of formula I include K2[SiF6]:Mn4+、K2[TiF6]:Mn4+、K2[SnF6]:Mn4+、Cs2[TiF6]:Mn4+、Rb2[TiF6] :Mn4+、Cs2[SiF6] :Mn4+、Rb2[SiF6] :Mn4+、Na2[TiF6]:Mn4+、Na2[ZrF6]:Mn4+、K3[ZrF7]:Mn4+、K3[BiF6]:Mn4+、K3[YF6]:Mn4+、K3[LaF6]:Mn4+、K3[GdF6]:Mn4+、K3[NbF7]:Mn4+、K3[TaF7]:Mn4+. In a particular embodiment, the precursor of formula I is K2SiF6:Mn4+。
The phosphor precursor may be ground by grinding techniques known in the art. Non-limiting examples of milling techniques may include planetary milling, attrition milling, ball milling, jet milling, atomizer techniques, or combinations thereof. In one embodiment, the phosphor precursors are ball milled. Other milling (grinding) techniques that provide a reduced particle size (e.g., D50 particle size less than about 30 microns) may be used. In one embodiment, the milling is performed under vacuum or in an inert environment. Thus, it should be understood that any method of reducing the particle size of the phosphor precursor by these mechanical means should not depart from the scope of the present invention.
The particles of the ground or milled phosphor precursor of formula I are rotated at a rotational speed for a selected period of time, depending in part on the particle size of the particles prior to milling and the desired particle size of the resulting particles after milling. In one embodiment, the particles have a particle size distribution of less than about 30 microns D50 value (or D50 particle size) after grinding. In particular embodiments, the milled particles have a D50 particle size of from about 10 microns to about 20 microns, more particularly, from about 12 microns to about 18 microns.
In some embodiments, milling may be with a liquid medium. The liquid medium can include a ketone (e.g., acetone), an alcohol, an ester (e.g., t-butyl acetate), water, an acid, or a mixture thereof. During milling, the phosphor composition of formula I typically reacts with the liquid medium through hydrolysis and redox reactions and exhibits reduced performance. For example, Table 1 shows K upon milling with acetone2[SiF6]:Mn4+The quantum efficiency of (PFS) decreases with time. In addition to the sensitivity of the phosphor of formula I to many liquid media, milling can also introduce defects into the phosphor precursor of formula I, thereby reducing the performance of the resulting phosphor.
Alternatively, upon dry grinding in dry air or other environment, phosphor particle destruction increases the susceptibility of these particles to hydrolysis and undergoes redox reactions with moisture in air. This may also reduce the performance of the phosphor.
Thus, according to embodiments of the present invention, the particles are treated after milling to increase the resulting Mn4+The performance and stability (quantum efficiency, thermal stability, humidity stability, flux stability and color stability) of the doped phosphor. In one embodiment, the milled particles are contacted with a fluorine-containing oxidizing agent in gaseous form at elevated temperature.
The elevated temperature at which the particles are contacted with the fluorine-containing oxidizing agent is any temperature in the range of from about 200 ℃ to about 700 ℃, specifically from about 350 ℃ to about 600 ℃, in some embodiments from about 200 ℃ to about 700 ℃ during the contacting. In various embodiments of the invention, the temperature is at least 100 ℃, specifically at least 225 ℃, more specifically at least 350 ℃. The phosphor precursor particles are contacted with the oxidizing agent for a time sufficient to enhance the performance and stability of the resulting phosphor. Time and temperature are related and can be adjusted together, for example, to increase time while decreasing temperature, or to increase temperature while decreasing time. In particular embodiments, the time is at least 1 hour, specifically at least 4 hours, more specifically at least 6 hours, and most specifically at least 8 hours.
After holding at the elevated temperature for the desired time, the temperature may be lowered at a controlled rate while maintaining the oxidizing atmosphere for the initial cool down time. After the initial cooling time, the cooling rate may be controlled at the same or different rate, or not. In some embodiments, the cooling rate is controlled at least until a temperature of 200 ℃ is reached. In other embodiments, the cooling rate is controlled at least until the temperature of the safe purge atmosphere is reached. For example, the temperature may be reduced to about 50 ℃ before purging the fluorine atmosphere begins.
Lowering the temperature at a controlled rate of 5 deg.C/min or less results in a phosphor product with superior performance compared to lowering the temperature at a rate of 10 deg.C/min. In various embodiments, the rate can be controlled at a rate of 5 deg.C/minute or less, specifically 3 deg.C/minute or less, and more specifically 1 deg.C/minute or less.
The time elapsed for lowering the temperature at a controlled rate is related to the contact temperature and the cooling rate. For example, at a contact temperature of 540 ℃ and a cooling rate of 10 ℃/minute, the time to control the cooling rate can be less than 1 hour, and subsequently, the temperature can be lowered to the purge or ambient temperature without external control. The cooling time can be less than 2 hours when the contact temperature is 540 ℃ and the cooling rate is less than or equal to 5 ℃/min. The cooling time can be less than 3 hours when the contact temperature is 540 ℃ and the cooling rate is less than or equal to 3 ℃/min. The cooling time can be less than 4 hours when the contact temperature is 540 ℃ and the cooling rate is less than or equal to 1 ℃/minute. For example, the temperature may be reduced to about 200 ℃ with controlled cooling, and then control may be discontinued. After the controlled cool down period, the temperature may be decreased at a higher or lower rate than the initial control rate.
The fluorine-containing oxidizing agent can be F2、HF、SF6、BrF5、NH4HF2、NH4F、KF、AlF3、SbF5、ClF3、BrF3、KrF、XeF2、XeF4、NF3、SiF4、PbF2、ZnF2、SnF2、CdF2Or a combination thereof. In a particular embodiment, the fluorine-containing oxidizing agent is F2. The amount of oxidizing agent in the atmosphere can be varied to obtain stable phosphor particles, particularly in combination with varying time and temperature. In the presence of F as fluorine-containing oxidizing agent2When the atmosphere contains at least 0.5% F2Although lower concentrations may be effective in some embodiments. In particular, the atmosphere may comprise at least 5% F2More specifically, at least 20% F2. The atmosphere may additionally comprise nitrogen, helium, neon, argon, krypton, xenon, in any combination with a fluorine-containing oxidizing agent. In particular embodiments, the atmosphere consists of about 20% F2And about 80% nitrogen.
The manner in which the ground particles are contacted with the fluorine-containing oxidizing agent is not critical and can be accomplished in any manner sufficient to convert the precursor particles into a stable phosphor having the desired properties. In some embodiments, the chamber containing the precursor particles may be charged and then sealed such that an overpressure is created when the chamber is heated, while in other embodiments, the fluorine and nitrogen mixture is flowed throughout the annealing process, thereby ensuring a more uniform pressure. In some embodiments, an additional dose of fluorine-containing oxidizing agent may be introduced after a period of time.
In one embodiment, after contacting the particles with the fluorine-containing oxidizing agent, the milled particles are further treated with a saturated solution of a composition of formula II in aqueous hydrofluoric acid, as described in US 8,252,613.
Ax [MFy] (II)
The temperature at which the phosphor is contacted with the solution is about 20 ℃ to about 50 ℃. The time required to treat the phosphor is about 1 minute to about 5 hours, and specifically about 5 minutes to about 1 hour. The concentration of hydrofluoric acid in the aqueous HF solution is about 20 wt% to about 70 wt%, specifically about 40 wt% to about 70 wt%. Lower concentration solutions can result in lower yields of phosphor.
Any numerical value described herein includes all values from the lower value to the upper value in 1 unit increments provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if it is stated that the amount of a component or a value of a process variable (e.g., temperature, pressure, time, etc.) is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, then it is intended in this specification to expressly recite a value, for example, from 15 to 85, from 22 to 68, from 43 to 51, from 30 to 32, etc. For values less than 1, 1 unit is suitably considered to be 0.0001, 0.001, 0.01, or 0.1. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner.
In another aspect, the invention relates to a method comprising grinding phosphor precursor particles and then contacting the ground precursor particles with a fluorine-containing oxidizing agent at an elevated temperature to form Mn4+A doped phosphor, the precursor being selected from
(A) A2[MF5]:Mn4+Wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof; wherein M is selected from Al, Ga, In and combinations thereof;
(B) A3[MF6]:Mn4+wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof; wherein M is selected from Al, Ga, In and combinations thereof;
(C) Zn2[MF7]:Mn4+wherein M is selected from the group consisting of Al, Ga, In, and combinations thereof;
(D) A[In2F7]:Mn4+wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof;
(E) A2[MF6]:Mn4+wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof; wherein M is selected from Ge, Si, Sn, Ti, Zr, and combinations thereof;
(F) E[MF6]:Mn4+wherein E is selected from Mg, Ca, Sr, Ba, Zn, and combinations thereof; wherein M is selected from Ge, Si, Sn, Ti, Zr, and combinations thereof;
(G) Ba0.65Zr0.35F2.70:Mn4+(ii) a And
(H) A3[ZrF7]:Mn4+wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof.
The time, temperature and fluorine-containing oxidizing agent of the process are as described above.
Mn of the formula I and of the groups (A) to (H)4+The amount of manganese in the doped precursor neutralized phosphor product is from about 0.3 wt% to about 2.5 wt% (about 1.2 mol% to about 10 mol%) based on the total weight of the precursor or stabilized phosphor. In some embodiments, the amount of manganese is from about 0.3% by weight to about 1.5% by weight (about 1.2% mol to about 6% mol), specifically from about 0.50% by weight to about 0.85% by weight (about 2% mol to about 3.4% mol), more specifically from about 0.65% by weight to about 0.75% by weight (about 2.6% mol to about 3% mol). In other embodiments, the amount of manganese is about 0.75% to 2.5% by weight (about 3% to about 10% by mol), specifically about 0.9% to 1.5% by weight (about 3.5% to about 6% by mol), more specifically about 0.9% to about 1.4% by weight (about 3.0% to about 5.5% by mol), even more specifically about 0.9% to about 1.3% by weight (about 3.5% to about 5.1% by mol).
A lighting device or light emitting assembly or lamp 10 of one embodiment of the present invention is shown in fig. 1. The lighting device 10 includes a semiconductor radiation source, shown as a Light Emitting Diode (LED) chip 12, and leads 14 electrically connected to the LED chip. The leads 14 may be thin wires supported by a thicker lead frame 16, or the leads may be self-supporting electrodes and the lead frame may be omitted. The leads 14 provide current to the LED chip 12 and thus cause it to emit radiation.
The lamp may comprise any semiconductor blue or UV light source capable of producing white light when its emitted radiation is directed onto the phosphor. In one embodiment, the semiconductor light source is a blue emitting LED doped with different impurities. Thus, an LED may comprise any suitable III-V, II-VI or IV-IV semiconductor layer based and have about 250 to 550nm semiconductor diodes emitting wavelengths. In particular, the LED may include at least one semiconductor layer comprising GaN, ZnSe, or SiC. For example, the LED may comprise the formula IniGajAlkN (wherein 0 ≦ I, 0 ≦ j, 0 ≦ k, and I + j + k =1) represents a nitride semiconductor having an emission wavelength greater than about 250nm and less than about 550 nm. In particular embodiments, the chip is a near uv or blue emitting LED having a peak emission wavelength of about 400nm to about 500 nm. These LED semiconductors are known in the art. For convenience, the radiation source is described herein as an LED. However, the term as used herein is intended to include all semiconductor radiation sources, including, for example, semiconductor laser diodes. Additionally, while the general discussion of exemplary structures of the invention discussed herein refers to an inorganic LED-based light source, it should be understood that the LED chip may be replaced by another radiation source unless otherwise noted, and any reference to a semiconductor, semiconductor LED, or LED chip merely represents any suitable radiation source, including but not limited to an organic light emitting diode.
In the lighting device 10, the phosphor material or composition 22 is radiationally coupled to the LED chip 12. Radiation coupling refers to the joining of elements together so that radiation is transmitted from one element to another. The phosphor composition 22 is deposited on the LED 12 by any suitable method. For example, a water-based suspension of phosphor may be formed and applied to the LED surface as a phosphor layer. In one such method, a silicone paste with phosphor particles randomly suspended therein is disposed around the LED. This approach is merely exemplary of possible locations for the phosphor composition 22 and the LED 12. Thus, the phosphor composition 22 may be coated on the light emitting surface of the LED chip 12, or directly thereon, by coating and drying the phosphor suspension on the LED chip 12. In the case of silicone-based suspensions, the suspension is cured at a suitable temperature. Both the shell 18 and the encapsulant 20 should be transparent to allow the transmission of white light 24 through those elements. Although not intended to be limiting, in some embodiments, the D50 particle size of the phosphor composition is from about 1 to about 50 microns, specifically, from about 10 to about 35 microns.
In other embodiments, the phosphor composition 22 is dispersed within the encapsulant material 20, rather than being formed directly on the LED chip 12. The phosphor (in powder form) may be dispersed within a single region of the encapsulant material 20, or throughout the entire volume of the encapsulant material. The blue light emitted by the LED chip 12 mixes with the light emitted by the phosphor composition 22 and the mixed light appears as white light. If the phosphor is to be dispersed within the encapsulant material 20, the phosphor powder may be added to a polymer or silicone precursor and the mixture may then be cured to solidify the polymer or silicone material after or before the mixture is loaded onto the LED chip 12. Other known phosphor dispersion methods, such as transferring a load, may also be used.
In some embodiments, the encapsulant material 20 has a refractive index R, and in addition to the phosphor composition 22, includes a diluent material having an absorbance of less than about 5% and a refractive index R + -0.1. The diluent material has a refractive index of 1.7 or less, specifically 1.6 or less, more specifically 1.5 or less. In a specific embodiment, the diluent material is of formula II Ax [MFy]And has a refractive index of about 1.4. The addition of an optically inert material to the phosphor/silicone mixture may produce a more gradual distribution of the luminous flux through the phosphor/encapsulant mixture and may produce less damage to the phosphor. Suitable materials for the diluent include those having a composition of about 1.38 (AlF)3And K2NaAlF6) To about 1.43 (CaF)2) Of refractive index, e.g. LiF, MgF2、CaF2、SrF2、AlF3、K2NaAlF6、KMgF3、CaLiAlF6、K2LiAlF6And K2SiF6And a polymer having a refractive index of about 1.254 to about 1.7. Non-limiting examples of polymers suitable for use as diluents include polycarbonates, polyesters, nylons, polyetherimides, polyetherketones, and polymers derived from styrene, acrylate, methacrylate, vinyl acetate, ethylene, propylene oxide, and ethylene oxide monomers and copolymers thereof, including halogenated and non-halogenated derivatives. These polymer powders can be added directly to the silicone encapsulant before the silicone is cured.
In another embodiment, the phosphor composition 22 is coated on the surface of the shell 18, rather than being formed on the LED chip 12. The phosphor composition is preferably coated on the inner surface of the shell 18, although the phosphor may be coated on the outer surface of the shell if desired. The phosphor composition 22 may be coated on the entire surface of the shell or only on top of the surface of the shell. The UV/blue light emitted by the LED chip 12 mixes with the light emitted by the phosphor composition 22 and the mixed light appears as white light. Of course, the phosphor may be located in any two or all three locations, or in any other suitable location, such as separate from the shell or bonded to the LED.
Fig. 2 illustrates a second architecture of the system according to the invention. Corresponding reference numerals (e.g., 12 in fig. 1, 112 in fig. 2) of fig. 1-4 relate to corresponding structure in the various figures, unless otherwise noted. The structure of the embodiment of fig. 2 is similar to that of fig. 1, except that the phosphor composition 122 is interspersed within the encapsulant material 120, rather than being formed directly on the LED chip 112. The phosphor (in powder form) may be dispersed within a single region of the encapsulant material, or throughout the entire volume of the encapsulant material. The radiation emitted by the LED chip 112 (indicated by arrows 126) mixes with the light emitted by the phosphor 122, and the mixed light appears as white light 124. If the phosphor is to be dispersed within the encapsulant material 120, a phosphor powder may be added to the polymer precursor and loaded around the LED chip 112. The polymer or silicone precursor can then be cured to solidify the polymer or silicone. Other known phosphor dispensing methods, such as transfer molding, may also be used.
Fig. 3 illustrates a third possible architecture of the system according to the invention. The structure of the embodiment shown in fig. 3 is similar to that of fig. 1, except that the phosphor composition 222 is coated on the surface of the cover 218, rather than being formed over the LED chip 212. The phosphor composition 222 is preferably coated on the inner surface of the cover 218, although the phosphor may be coated on the outer surface of the cover if desired. The phosphor composition 222 may be coated on the entire surface of the shade or only on top of the surface of the shade. Radiation 226 emitted by the LED chip 212 mixes with the light emitted by the phosphor composition 222, and the mixed light appears as white light 224. Of course, the structures of fig. 1-3 may be combined, and the phosphor may be located in any two or all three locations, or in any other suitable location, such as separate from the shade or bonded to the LED.
In any of the above structures, the lamp may also include a plurality of scattering particles (not shown) embedded in the encapsulant material. The scattering particles may comprise, for example, alumina or titania. The scattering particles effectively scatter the directed light emitted from the LED chip, preferably with a negligible amount of absorption.
As shown in the fourth structure in fig. 4, the LED chip 412 may be mounted in the reflective cup 430. Cup 430 may be made of or coated with a dielectric material, such as alumina, titania, or other dielectric powders known in the art, or coated with a reflective metal, such as aluminum or silver. The remainder of the structure of the embodiment of fig. 4 is the same as that of any of the previous figures, and may include two leads 416, a wire 432, and an encapsulant material 420. The reflective cup 430 is supported by the first lead 416 and electrically connects the LED chip 412 with the second lead 416 with a wire 432.
Another structure, particularly for backlighting applications, is a surface mount device ("SMD") type light emitting diode 550, as shown in fig. 5. Such SMDs are of a "side emission type" and have a light emission window 552 on a protruding portion of a light guide member 554. The SMD package may comprise an LED chip as defined above, and a phosphor material excited by light emitted from the LED chip. Other backlighting devices include, but are not limited to, televisions, computers, monitors, smart phones, tablet computers, and other devices having Mn including semiconductor light sources and color stabilization of the present invention4+Other hand held devices for doped phosphor displays.
When an LED emitting at 350 to 550nm and one or more other suitable phosphors are used, the resulting illumination system produces light having a white color. The lamp 10 may also include scattering particles (not shown) embedded in an encapsulant material. The scattering particles may comprise, for example, alumina or titania. The scattering particles effectively scatter the directed light emitted from the LED chip, preferably with a negligible amount of absorption.
Except for Mn4+Outside the doped phosphor, the doped phosphor is,the phosphor composition 22 may also include one or more other phosphors. When used in combination with a blue or near UV LED emitting radiation in the range of about 250nm to 550nm in a lighting device, the resulting light emitted by the assembly is white light. Other phosphors, such as green, blue, yellow, red, orange, or other colored phosphors, may be used in the mixture to tailor the white color of the resulting light and produce a particular spectral power distribution. Other materials suitable for use in the phosphor composition 22 include electroluminescent polymers such as polyfluorenes, preferably poly (9, 9-dioctylfluorene) and its copolymers such as 9,9 '-dioctylfluorene-bis-N, N' - (4-butylphenyl) diphenylamine copolymer (F8-TFB); poly (vinylcarbazole) and polyphenylacetylene and derivatives thereof. In addition, the light emitting layer may include blue, yellow, orange, green, or red phosphorescent dyes or metal complexes, or a combination thereof. Materials suitable for use as phosphorescent dyes include, but are not limited to, tris (1-phenylisoquinoline) iridium (III) (red dye), tris (2-phenylpyridine) iridium (green dye), and bis (2- (4, 6-difluorophenyl) pyridine-N, C2) iridium (III) (blue dye). Commercially available fluorescent and phosphorescent metal complexes available from ADS (American Dyes Source, Inc.). The ADS green dyes include ADS060GE, ADS061GE, ADS063GE and ADS066GE, ADS078GE and ADS090 GE. The ADS blue dyes include ADS064BE, ADS065BE and ADS070 BE. The ADS red dye comprises ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE and ADS077 RE.
Suitable phosphors for the phosphor composition 22 include, but are not limited to:
Figure 291546DEST_PATH_IMAGE002
。
the ratio of individual phosphors in the phosphor mixture may vary depending on the characteristics of the desired light output. The relative proportions of the individual phosphors in the different embodiment phosphor blends may be adjusted so that, when their emissions are mixed and used in an LED lighting device, predetermined x and y values on the CIE chromaticity diagram are producedVisible light. As described above, white light is preferably generated. For example, the white light may have an x value of about 0.20 to about 0.55 and a y value of about 0.20 to about 0.55. However, as noted above, the precise nature and amount of each phosphor in the phosphor composition can vary according to the end user needs. For example, the material may be used in LEDs for backlighting Liquid Crystal Displays (LCDs). In this application, the LED color point is tuned approximately based on the white, red, green and blue colors desired after passing through the LCD/color filter combination. The list of possible phosphors for mixing given here is not meant to be exhaustive, these Mn's being4+The doped phosphor may be mixed with various phosphors having different emissions to obtain a desired spectral power distribution.
Mn of the invention4+Doped phosphors may also be used in applications other than those described above. For example, the material may be used as a phosphor for fluorescent lamps, for cathode ray tubes, for plasma display devices, or for Liquid Crystal Displays (LCDs). The material may also be used as a scintillator for electromagnetic calorimeters, for gamma-ray cameras, for computed tomography scanners or for lasers. These uses are exemplary only and not limiting.
Examples
The following examples are illustrative only and should not be construed as any limitation on the scope of the claimed invention.
Manganese (Mn)4+) Doping with K2SiF6Synthesized according to the method described in the cited us patent 7,497,973 in HF solution with a drying temperature of about 70 ℃.
Ball milling of K in acetone2SiF6:Mn4+72.6 micron D50 particles for 20 minutes. Table 1 shows the results of the preliminary synthesis of K2SiF6:Mn4+Comparison of K after 5 and 20 minutes of milling2SiF6:Mn4+The quantum efficiency of (2) is decreased.
TABLE 1
Sample grinding time (minutes) D50 particle size (micrometer) QE (relative) Abs
0 (initial synthesis) 72.6 100% 90%
5 61.7 94% 89%
20 22.3 86% 70%
Example 1:
particles having a particle size of 46 microns D50 and containing 0.76 wt% Mn based on the total weight of the precursor material of 15g of manganese doped potassium fluorosilicate (PFS: Mn) precursor K2SiF6:Mn4+Add to a 250 ml nalgene bottle containing dry grinding media and seal in the bottle. The bottle was placed on a roller mill for 15 minutes. The milled precursor was removed from the bottle, the precursor having 16 micron D50 particles.
The milled precursor particles are then placed into the furnace chamber. The furnace chamber was evacuated and charged with a gas containing 20% F2 /80% N2Is filled in. The chamber was then heated to 540 ℃. After the precursor was annealed for 8 hours, the chamber was allowed to cool to room temperature. The fluorine-nitrogen mixture is evacuated, the chamber is filled with nitrogen and vented several times to ensure complete removal of fluorine before opening the chamberAnd (4) qi. Then, the mixture was passed through a column containing 100mL of K2SiF6Saturated solution (initially by addition of ~ 5g K in 40% HF at room temperature2SiF6Prepared by stirring and filtering the solution) was placed in a teflon beaker with the powder (~ 10g) and K was used2SiF6The saturated solution treated the annealed PFS powder. The suspension was stirred slowly, filtered, washed 3-5 times in acetone and the filtrate was dried under vacuum.
Example 2:
particles having a particle size of 46 microns D50 and containing 0.76 wt% Mn based on the total weight of the precursor material of 15g of manganese doped potassium fluorosilicate (PFS: Mn) precursor K2SiF6:Mn4+Add to a 250 ml nalgene bottle containing dry grinding media and seal in the bottle. The bottle was placed on a roller mill for 15 minutes. The milled precursor was removed from the bottle, the precursor having between 24 and 30 micron particles of D50. Table 2 shows that the QE of the PFS: Mn precursor decreased after milling.
The milled precursor particles are then placed into the furnace chamber. The furnace chamber was evacuated and charged with a gas containing 20% F2 /80% N2Is filled in. The chamber was then heated to 540 ℃. After the precursor was annealed for 8 hours, the chamber was allowed to cool to room temperature. The fluorine nitrogen mixture was evacuated, the chamber was filled with nitrogen and vented several times to ensure complete removal of fluorine gas before opening the chamber. Then, the mixture was passed through a column containing 100mL of K2SiF6Saturated solution (initially by addition of ~ 5g K in 40% HF at room temperature2SiF6Prepared by stirring and filtering the solution) was placed in a teflon beaker with the powder (~ 10g) and K was used2SiF6Saturated solution treatment (wet treatment) the annealed PFS powder. The suspension was stirred slowly, filtered, washed 3-5 times in acetone and the filtrate was dried under vacuum.
Table 2 shows PFS samples of example 1 and example 2 with a commercial phosphor K2SiF6Quantum Efficiency (QE) and stability (examined under high-throughput conditions) of Mn (comparative example). The milled and post-treated samples showed improved Quantum Efficiency (QE) and lifetime compared to the PFS of the comparative example and the as-synthesized PFS samples, and experienced significantly less damage. It was also observed for example 2 that annealing increased the QE of the PFS powder by 23% -28%,the absorbance at 300nm is reduced and the lifetime is improved. In addition, the wet treatment improves the stability of HTHH (high temperature high humidity). The HTHH destruction or loss improved from greater than 45% to less than 10%.
TABLE 2
Figure DEST_PATH_IMAGE003
While only certain features of the invention have been illustrated and described herein, many modifications and changes will occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.

Claims (7)

1. A method of synthesizing a manganese doped phosphor, the method comprising:
milling particles of a phosphor precursor of formula I; and is
Ax [MFy]:Mn4+ (I)
Contacting the milled particles with a fluorine-containing oxidizing agent, F, at any temperature in the range of 200 ℃ to 700 ℃2、SF6、BrF5、NH4HF2、NH4F、KF、AlF3、SbF5、ClF3、BrF3、KrF、XeF2、XeF4、NF3、SiF4、PbF2、ZnF2、SnF2、CdF2Or a combination thereof,
wherein the content of the first and second substances,
a is Li, Na, K, Rb, Cs or the combination thereof;
m is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof;
x is [ MFy]The absolute value of the charge of the ion;
y is 5, 6 or 7.
2. The method of claim 1 wherein the particles of the phosphor precursor of formula I have a particle size distribution after milling of less than a 30 micron D50 value.
3. The method of claim 1, wherein the particles of the phosphor precursor of formula I have a particle size distribution with a D50 value of 10 microns to 25 microns after milling.
4. The method of claim 1 wherein said fluorine-containing oxidizing agent comprises F2。
5. The method of claim 1, further comprising contacting the milled particles with a saturated solution of a compound of formula II in aqueous hydrofluoric acid after contacting the milled particles with the fluorine-containing oxidizing agent,
Ax [MFy] (II)。
6. the method of claim 1, wherein the phosphor precursor is K2SiF6:Mn4+。
7. A method of synthesizing a manganese doped phosphor, the method comprising:
grinding particles of a phosphor precursor, wherein the precursor is selected from the group consisting of:
(A) A2[MF5]:Mn4+wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof, and M is selected from Al, Ga, In and combinations thereof;
(B) A3[MF6]:Mn4+wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof, and M is selected from Al, Ga, In and combinations thereof;
(C) Zn2[MF7]:Mn4+wherein M is selected from the group consisting of Al, Ga, In, and combinations thereof;
(D) A[In2F7]:Mn4+wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof;
(E) A2[MF6]:Mn4+wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof, and M is selected from Ge, Si, Sn, Ti, Zr and combinations thereof;
(F) E[MF6]:Mn4+wherein E is selected from Mg, Ca, Sr, Ba, Zn and combinations thereof, and M is selected from Ge, Si, Sn, Ti, ZrAnd combinations thereof;
(G) Ba0.65Zr0.35F2.70:Mn4+(ii) a And
(H) A3[ZrF7]:Mn4+wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof, and
contacting the particles with a fluorine-containing oxidizing agent, F, at any temperature in the range of 200 ℃ to 700 ℃2、SF6、BrF5、NH4HF2、NH4F、KF、AlF3、SbF5、ClF3、BrF3、KrF、XeF2、XeF4、NF3、SiF4、PbF2、ZnF2、SnF2、CdF2Or a combination thereof.
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